Hydroconversion of renewable feedstocks

ABSTRACT

A hydrocarbon conversion process comprises contacting a renewable feedstock under hydroprocessing conditions with a bulk catalyst to form oleochemicals such as fatty alcohols, esters, and normal paraffins. Advantageously, the reaction conditions can be selected to directly convert the renewable feedstock to the desired product(s).

TECHNICAL FIELD

The application relates generally to a process for converting renewablefeedstocks to oleochemicals such as fatty alcohols, esters, and normalparaffins by contacting the feedstock with a bulk multi-metalliccatalyst under hydroprocessing conditions.

BACKGROUND

Fossil fuels are a finite, non-renewable resource formed from decayedplants and animals that have been converted to crude oil, coal, naturalgas, or heavy oils by exposure to heat and pressure in the earth's crustover hundreds of millions of years. However, as the world's petroleumresources are depleting coupled with its ever-increasing prices, manyindustries worldwide have been looking into renewable/sustainable rawmaterials to replace petroleum-based materials in their manufacturingprocesses.

Industrial oleochemicals are useful in the production of surfactants,lubricants, fuels, plastics, and the like. Oleochemicals include, butare not limited to, fatty alcohols, esters and paraffins. Providingefficient processes for directly converting renewable materials intosuch products would be highly desirable.

SUMMARY

In one aspect, there is provided a hydrocarbon conversion processcomprising contacting a renewable feedstock, under hydroprocessingconditions, with a bulk catalyst to form an effluent and recovering afatty alcohol fraction from the effluent, wherein the hydroprocessingconditions include a temperature of from 383° F. to 464° F. (195° C. to240° C.) and a total reaction pressure of from 800 to 2000 psig (5.5 to13.8 MPa gauge).

In another aspect, there is provided a hydrocarbon conversion processcomprising contacting a renewable feedstock, under hydroprocessingconditions, with a bulk catalyst to form an effluent and recovering analiphatic monoester fraction from the effluent, wherein thehydroprocessing conditions include a temperature of from 383° F. to 464°F. (195° C. to 240° C.) and a total reaction pressure of from 800 to2000 psig (5.5 to 13.8 MPa gauge).

In yet another aspect, there is provided hydrocarbon conversion processcomprising contacting a renewable feedstock, under hydroprocessingconditions, with a bulk catalyst to form an effluent and recovering ahydrocarbon fraction comprising normal paraffins from the effluent,wherein the hydroprocessing conditions include a temperature of from491° F. to 662° F. (255° C. to 350° C.) and a total reaction pressure offrom 800 to 2000 psig (5.5 to 13.8 MPa gauge).

DETAILED DESCRIPTION

The following terms will be used throughout the specification and willhave the following meanings unless otherwise indicated.

The term “renewable feedstock” is meant to include feedstocks other thanthose obtained from crude oil.

The term “oleochemical” refers to a chemical that isbiologically-derived, i.e., from a renewable resource of biologicalorigin. Such a term is generally accepted as being exclusive of fossilfuels.

A “middle distillate” is a hydrocarbon product having a boiling range offrom 250° F. to 1100° F. (121° C. to 593° C.). The term “middledistillate” includes the diesel, heating oil, jet fuel, and keroseneboiling range fractions. It may also include a portion of naphtha orlight oil. A “jet fuel” is a hydrocarbon product having a boiling rangein the jet fuel boiling range. The term “jet fuel boiling range” refersto hydrocarbons having a boiling range of from 280° F. to 572° F. (138°C. to 300° C.). The term “diesel fuel boiling range” refers tohydrocarbons having a boiling range of from 250° F. to 1000° F. (121° C.to 538° C.). The “boiling range” is the 10 vol. % boiling point to thefinal boiling point (99.5 vol. %), inclusive of the end points, asmeasured by ASTM D2887-08 (“Standard Test Method for Boiling RangeDistribution of Petroleum Fractions by Gas Chromatography”).

The term “triglyceride,” refers to class of molecules having the generalformula

wherein R, R¹ and R² are independently aliphatic residues having from 6to 22 carbon atoms (e.g., from 8 to 20 carbon atoms, or from 10 to 16carbon atoms). The term “aliphatic” means a straight (i.e., un-branched)or branched, substituted or un-substituted hydrocarbon chain that iscompletely saturated or that contains one or more units of unsaturation.

The term “fatty alcohol” refers to primary aliphatic alcohols generallyhaving from 8 to 24 carbon atoms, usually from 8 to 18 carbon atoms.

The term “aliphatic monoester” refers to compounds having the generalformula (2):

wherein R³ and R⁴ are independently alkyl moieties, R⁴ is an alkylmoiety having at least 8 carbon atoms, and the total carbon number ofthe aliphatic monoester is at least 14. In some embodiments, thealiphatic ester has from 16 to 40 carbon atoms (e.g., from 18 to 36, orfrom 20 to 34 carbon atoms). Such esters can be useful as lubricants.

The term “paraffin” refers to any saturated hydrocarbon compound, i.e.,an alkane having the formula C_(n)H_((2n+2)) where n is a positivenon-zero integer.

The term “normal paraffin” refers to a saturated straight chainhydrocarbon.

The term “isoparaffin” refers to a saturated branched chain hydrocarbon.

The term “hydroconversion” can be used interchangeably with the term“hydroprocessing” and refers to any process that is carried out in thepresence of hydrogen and a catalyst. Such processes include, but are notlimited to, methanation, water gas shift reactions, hydrogenation,hydrotreating, hydrodesulfurization, hydrodenitrogenation,hydrodeoxygenation, hydrodemetallation, hydrodeoxygenation,hydrodearomatization, hydroisomerization, hydrodewaxing andhydrocracking including selective hydrocracking.

The term “isomerizing” refers to catalytic process in which a normalparaffin is converted at least partially into an isoparaffin. Suchisomerization generally proceeds by way of a catalytic route.

The term “bulk catalyst” can be used interchangeably with “unsupportedcatalyst,” or “self-supported catalyst,” meaning that the catalystcomposition is NOT of the conventional catalyst form which has apreformed, shaped catalyst support which is then loaded with metalcompounds via impregnation or deposition catalyst. In one embodiment,the bulk catalyst is formed through precipitation. In anotherembodiment, the bulk catalyst has a binder incorporated into thecatalyst composition. In yet another embodiment, the bulk catalyst isformed from metal compounds and without any binder.

The term “catalyst precursor” refers to a compound containing at least apromoter metal selected from Group IIA, Group IIB, Group IVA, Group VIIImetals and combinations thereof (i.e., one or more Group IIA metals, oneor more Group IIB metals, one or more Group IVA metals, one or moreGroup VIII metals, and combinations thereof); at least a Group VIBmetal; an oxide or a hydroxide; and, optionally, one or more organicoxygen-containing ligands, and which compound can be catalyticallyactive after sulfidation as a hydroprocessing catalyst.

The term “Group IIA” or “Group IIA metal” refers to beryllium (Be),magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra),and combinations thereof in their elemental, compound, or ionic form.

The term “Group IIB” or “Group IIB metal” refers to zinc (Zn), cadmium(Cd), mercury (Hg), and combinations thereof in their elemental,compound, or ionic form.

The term “Group IVA” or” “Group IVA metal” refers to germanium (Ge), tin(Sn) or lead (Pb), and combinations thereof in their elemental,compound, or ionic form.

The term “Group VIB” or “Group VIB metal” refers to chromium (Cr),molybdenum (Mo), tungsten (W), and combinations thereof in theirelemental, compound, or ionic form.

The term “Group VIII” or “Group VIII metal” refers to iron (Fe), cobalt(Co), nickel (Ni), ruthenium (Ru), rhenium (Re), palladium (Pd), osmium(Os), iridium (Ir), platinum (Pt), and combinations thereof in theirelemental, compound, or ionic form.

When used herein, the Periodic Table of the Elements refers to theversion published by the CRC Press in the CRC Handbook of Chemistry andPhysics, 88th Edition (2007-2008). The names for families of theelements in the Periodic Table are given here in the Chemical AbstractsService (CAS) notation.

The term “conversion” refers to the amount of triglycerides in the feedthat is converted to compounds other than triglycerides. Conversion isexpressed as a weight percentage based on triglycerides in the feed.“Selectivity” is expressed as a weight percent based on convertedtriglycerides. It should be understood that each compound converted fromtriglycerides has an independent selectivity and that selectivity isindependent from conversion.

Feed

The renewable feedstocks that can be used include any of those whichcomprise triglycerides. The feedstock generally originates from abiomass source selected from the group consisting of crops, vegetables,microalgae, animal fats, and combinations thereof. The feedstockgenerally comprises at least 25 wt. % triglycerides (e.g., at least 50wt. %, 75 wt. %, 90 wt. %, or 95 wt. % triglycerides). Those of skill inthe art will recognize that generally any biological source of lipidscan serve as the biomass from which the feedstock can be obtained. Itwill be further appreciated that some such sources are more economicaland more amenable to regional cultivation, and also that those sourcesfrom which food is not derived can be additionally attractive (so as notto be seen as competing with food). Exemplary feedstocks include, butare not limited to canola oil, coconut oil, palm oil, palm kernel oil,peanut oil, rapeseed oil, soybean oil, and the like.

Hydroprocessing Catalyst

The bulk catalyst is derived from a catalyst precursor. The catalystprecursor can be a hydroxide or oxide material, prepared from at least apromoter metal precursor feed and at least a Group VIB metal precursorfeed. “Promoter metal” can be used interchangeably with M^(P), referringto a material that enhances the activity of a catalyst (as compared to acatalyst without the promoter metal, e.g., a catalyst with just a GroupVIB metal). The bulk or unsupported catalyst precursor made can beconverted into a hydroconversion bulk catalyst (becoming catalyticallyactive) upon sulfidation.

Further details regarding the description of the catalyst precursor andthe bulk catalyst formed thereof are described in a number of patentsand patent applications, including U.S. Pat. Nos. 6,156,695; 6,162,350;6,274,530; 6,299,760; 6,566,296; 6,620,313; 6,635,599; 6,652,738;6,758,963; 6,783,663; 6,860,987; 7,179,366; 7,229,548; 7,232,515;7,288,182; 7,544,285, 7,615,196; 7,803,735; 7,807,599; 7,816,298;7,838,696; 7,910,761; 7,931,799; 7,964,524; 7,964,525; 7,964,526;8,058,203; and U.S. Pat. Application Publication Nos. 2007/0090024,2009/0107886, 2009/0107883, 2009/0107889 and 2009/0111683.

In one embodiment, the catalyst precursor is a bulk multi-metallicoxide, comprising of at least one Group VIII non-noble material and atleast two Group VIB metals. In one embodiment, the ratio of Group VIBmetal to Group VIII non-noble metal in the precursor ranges from about10:1 to about 1:10. In another embodiment, the oxide catalyst precursoris represented by the formula (3):

(X)_(b)(Mo)_(c)(W)_(d)O_(f)   (3)

wherein X is Ni or Co, the molar ratio of b: (c+d) is 0.5:1 to 3:1(e.g., 0.75:1 to 1.5:1, or 0.75:1 to 1.25:1), the molar ratio of c: dis >0.01:1 (e.g., greater than 0.1:1, 1:10 to 10:1, or 1:3 to 3:1), andf=[2b+6(c+d)]/2. In yet another embodiment, the oxide catalyst precursorfurther comprises one or more ligating agents L. The term “ligand” maybe used interchangeably with “ligating agent,” “chelating agent” or“complexing agent” or chelator, or chelant), referring to an additivethat combines with metal ions, e.g., Group VIB and/or promoter metals,forming a larger complex, e.g., a catalyst precursor.

In another embodiment, the catalyst precursor is in the form of ahydroxide compound, comprising of at least one Group VIII non-noblematerial and at least two Group VIB metals. In one embodiment, thehydroxide catalyst precursor is represented by the formula (4):

A_(v)[(M^(P))(OH)_(x)(L)^(n) _(y)]_(z)(M^(VIB)O₄)   (4)

wherein A is one or more monovalent cationic species; M^(P) is at leasta promoter metal with an oxidation state (P) of either +2 or +4depending on the promoter metal(s) being employed; L is one or moreoxygen-containing ligands, and L has a neutral or negative charge n≦0;M^(VIB) is at least a Group VIB metal having an oxidation state of +6;M^(P):M^(VIB) has an atomic ratio between 100:1 and1:100;v−2+P*z−x*z+n*y*z=0; and 0<v≦2; 0<x≦P; 0<y≦−P/n; 0<z. The catalystprecursor represented by formula (4) is charge-neutral. The term“charge-neutral” refers to the fact that the catalyst precursor carriesno net positive or negative charge.

In one embodiment, A is selected from the group consisting of an alkalimetal cation, an ammonium cation, an organic ammonium cation and aphosphonium cation.

In one embodiment, M^(P) has an oxidation state of either +2 or +4.M^(P) is at least one of a Group IIA metal, Group IIB metal, Group IVAmetal, Group VIII metal and combinations thereof. In one embodiment,M^(P) is at least a Group VIII metal with M^(P) having an oxidationstate P of +2. In another embodiment, M^(P) is selected from Group IIBmetals, Group IVA metals and combinations thereof. In one embodiment,M^(P) is selected from the group of Group IIB and Group VIA metals suchas zinc, cadmium, mercury, germanium, tin or lead, and combinationsthereof, in their elemental, compound, or ionic form. In anotherembodiment, M^(P) is a Group IIA metal compound, selected from the groupof magnesium, calcium, strontium and barium compounds. M^(P) can be insolution or in partly in the solid state, e.g., a water-insolublecompound such as a carbonate, hydroxide, fumarate, phosphate, phosphite,sulfide, molybdate, tungstate, oxide, or mixtures thereof

In one embodiment, the optional ligating agent L has a neutral ornegative charge n≦0. Examples of oxygen-containing ligating agents Linclude but are not limited to carboxylates, carboxylic acids,aldehydes, ketones, the enolate forms of aldehydes, the enolate forms ofketones, and hemiacetals; organic acid addition salts such as formicacid, acetic acid, propionic acid, maleic acid, malic acid, cluconicacid, fumaric acid, succinic acid, tartaric acid, citric acid, oxalicacid, glyoxylic acid, aspartic acid, alkane sulfonic acids such asmethanesulfonic acid and ethanesulfonic acid, aryl sulfonic acids suchas benzenesulfonic acid and p-toluenesulfonic acid and arylcarboxylicacids; carboxylate containing compounds such as maleate, formate,acetate, propionate, butyrate, pentanoate, hexanoate, dicarboxylate, andcombinations thereof.

In one embodiment, M^(VIB) is at least a Group VIB metal having anoxidation state of +6. In another embodiment, M^(VIB) is a mixture of atleast two Group VIB metals, e.g., molybdenum and tungsten. M^(VIB) canbe in solution or in partly in the solid state. In one embodiment,M^(P):M^(VIB) has a mole ratio of 10:1 to 1:10.

Embodiments of the process for making the unsupported or bulk catalystprecursor are as described in the references indicated above, andincorporated herein by reference. In one embodiment, the first step is amixing step wherein at least one Group IVB metal precursor feed and atleast one promoter metal precursor feed are combined together in aprecipitation step (also called co-gelation or co-precipitation),wherein a catalyst precursor is formed as a gel. The precipitation (or“co-gelation”) is carried out at a temperature and pH under which thepromoter metal compound and the Group VIB metal compound precipitate(e.g., forming a gel). In one embodiment, the temperature is from 25° C.to 350° C. and the pressure is from 0 to 3000 psig (0 to 20.7 MPagauge). The pH of the reaction mixture can be changed to increase ordecrease the rate of precipitation (co-gelation), depending on thedesired characteristics of the catalyst precursor product. In oneembodiment, the mixture is left at its natural pH during the reactionstep(s). In another embodiment, the pH is maintained in the range from 0to 12.

Hydroprocessing Conditions

The hydroprocessing conditions can be selected so that an overallconversion rate of triglycerides in the feedstock is at least 20 wt. %,(e.g., at least 50 wt. %, 60 wt. %, 70 wt. %, 80 wt. %, 90 wt. %, or 95wt. %). Suitable hydroprocessing conditions can include a temperature offrom 383° F. to 662° F. (195° C. to 350° C.), e.g., from 383° F. to 464°F. (195° C. to 240° C.), 491° F. to 662° F. (255° C. to 350° C.), orfrom 491° F. to 563° F. (255° C. to 295° C.); a total reaction pressureof from 500 to 2000 psig (3.4 to 13.8 MPa gauge), e.g., from 800 to 2000psig (5.5 to 13.8 MPa gauge), or from 1600 to 2000 psig (11.0 to 13.8MPa gauge); a liquid hourly space velocity (LHSV) of from 0.1 to 5 h¹,e.g., from 0.5 to 2 h¹; and a hydrogen feed rate of from 0.1 to 20MSCF/bbl (thousand standard cubic feet per barrel), e.g., from 1 to 10MSCF/bbl. Note that a feed rate of 10 MSCF/bbl is equivalent to 1781 LH₂/L feed.

The hydroprocessing process can be single-staged or multiple-staged. Inone embodiment, the process utilizes a single-stage system. Catalystsprepared from the catalyst precursor can be applied in any reactor type.In one embodiment, the catalyst is applied to a fixed bed reactor.

If desired, unreacted triglycerides can be recycled to the reactionsystem for further processing to maximize production of the desiredproduct(s).

Products

The effluent from the hydroprocessing zone will comprise a liquidportion and a gaseous portion. After hydroprocessing, the effluent canbe passed to one or more separators/fractionators for the removal of gasphase products (e.g., CO, CO₂, methane and propane) and separation ofone or more fully and/or partially deoxygenated product fractions (e.g.,n-paraffins, fatty alcohols and/or aliphatic monoesters) from the liquidportion. Different feedstocks will result in different carbondistributions of liquid products.

In one embodiment the liquid product is a product selected from thegroup of a fatty alcohol, an aliphatic monoester, and normal paraffins.In another embodiment, the product is a fatty alcohol, an aliphaticmonoester, or a combination thereof. The hydroprocessing conditions canbe selected from any parameter that influences the subsequent level ofthe desired product(s) in the effluent from the reactor. In one aspect,the hydroprocessing parameter is one that obtains a yield of a productin the reactant mixture, increases the yield of a product, optimizes theselectivity of products in the reactor, or is effective for a conversionof triglycerides in the reactor. In one embodiment, the hydroprocessingparameter is selected from the group consisting of a reactortemperature, a reactor pressure and combinations thereof

In some embodiments, the effluent comprises a fatty alcohol fraction. Insome embodiments, the effluent comprises at least 5 wt. % of a fattyalcohol (e.g., at least 10 wt. % of a fatty alcohol). In someembodiments, the effluent has a selectivity to a fatty alcohol of atleast 10% (e.g., at least 15%, 20%, or 25%).

In some embodiments, the effluent comprises an aliphatic monoesterfraction. In some embodiments, the effluent comprises at least 4 wt. %of an aliphatic monoester (e.g., at least 7 wt. %, 10 wt. % or 13 wt.%). In some embodiments, the effluent has a selectivity to an aliphaticmonoester of at least 10% (e.g., at least 12%, 15%, or 18%).

In some embodiments, the effluent comprises a hydrocarbon fractioncomprising normal paraffins. In some embodiments, the effluent comprisesat least 75 wt. % of normal paraffins (e.g., at least 80 wt. % normalparaffins). In some embodiments, the normal paraffins have from 8 to 24carbon atoms (e.g., from 12 to 18 carbon atoms).

Note that the normal paraffins can be utilized as a middle distillatefuel. However, subsequent isomerization of the normal paraffins toisoparaffins can provide a broader range of products, thereby making theprocess more universal and flexible.

Catalytic Isomerization

In some embodiments, such above-described processes can further comprisea step of catalytically isomerizing at least some of the normalparaffins to yield an isomerized product comprising isoparaffins. Insome embodiments, the step of catalytically isomerizing results insuperior fuel properties (e.g., cloud point, pour point etc.) relativeto those of the non-isomerized paraffinic product.

In some embodiments, the step of isomerizing is carried out using anisomerization catalyst. Suitable such isomerization catalysts caninclude, but are not limited to, Pt and/or Pd on a support. Suitablesupports include, but are not limited to, zeolites CIT-1, IM-5,SSZ-20,SSZ-23, SSZ-24, SSZ-25, SSZ-26, SSZ-31, SSZ-32, SSZ-32, SSZ-33,SSZ-35, SSZ-36, SSZ-37, SSZ-41, SSZ-42, SSZ-43, SSZ-44, SSZ-46, SSZ-47,SSZ-48, SSZ-51, SSZ-56, SSZ-57, SSZ-58, SSZ-59, SSZ-60, SSZ-61, SSZ-63,SSZ-64, SSZ-65, SSZ-67, SSZ-68, SSZ-69, SSZ-70, SSZ-71, SSZ-74, SSZ-75,SSZ-76, SSZ-78, SSZ-81, SSZ-82, SSZ-83, SSZ-86, SUZ-4, TNU-9, ZSM-5,ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, EMT-type zeolites, FAU-typezeolites, FER-type zeolites, MEL-type zeolites, MFI-type zeolites,MTT-type zeolites, MTW-type zeolites, MWW-type zeolites, TON-typezeolites, other molecular sieves materials based upon crystallinealuminophosphates such as SM-3, SM-7, SAPO-11, SAPO-31, SAPO-41, MAPO-11and MAPO-31. In some embodiments, the step of isomerizing involves a Ptand/or Pd catalyst supported on an acidic support material selected fromthe group consisting of beta or zeolite Y molecular sieves, silica,alumina, silica-alumina, and combinations thereof. For other suitableisomerization catalysts, see, e.g., U.S. Pat. Nos. 4,859,312; 5,158,665;and 5,300,210.

Isomerization conditions can include a temperature of from 200° F. to900° F. (93° C. to 482° C.), e.g., from 300° F. to 800° F. (149° C. to427° C.), or from 400° F. to 800° F. (204° C. to 427° C.); a totalreaction pressure of from 15 to 3000 psig (0.1 to 20.7 MPa gauge), e.g.,from 50 to 2500 psig (0.3 to 17.2 MPa gauge); a LHSV of from 0.1 to 10h⁻¹, e.g., from 0.25 to 5 h⁻¹; and a hydrogen gas treat rate of from 0.1to 30 MSCF/bbl, e.g., from 0.2 to 20 MSCF/bbl, or from 0.4 to 10MSCF/bbl.

With regard to the catalytic isomerization step described above, in someembodiments, the methods described herein can be conducted by contactingthe normal paraffins with a fixed stationary bed of catalyst, with afixed fluidized bed, or with a transport bed. In one embodiment, atrickle-bed operation is employed, wherein such feed is allowed totrickle through a stationary fixed bed, typically in the presence ofhydrogen. For an illustration of the operation of such catalysts, see,U.S. Pat. Nos. 6,204,426 and 6,723,889.

In some embodiments, the isomerized product comprises at least 10 wt. %isoparaffins (e.g., at least 30 wt. %, 50 wt. %, or 70 wt. %isoparaffins). In some embodiments, the isomerized product has anisoparaffin to normal paraffin mole ratio of at least 5:1 (e.g., atleast 10:1, 15:1, or 20:1).

In some embodiments, the isomerized product has a boiling range of from250° F. to 1100° F. (121° C. to 593° C.), e.g., from 280° F. to 572° F.(138° C. to 300° C.), or from 250° F. to 1000° F. (121° C. to 538° C.).

In some embodiments, the isomerized product is suitable (or bettersuited) for use as a transportation fuel. In some such embodiments, theisomerized product is mixed or admixed with existing transportationfuels in order to create new fuels or to modify the properties ofexisting fuels. Isomerization and blending can be used to modulate andmaintain pour point and cloud point of the fuel or other product atsuitable values. In some embodiments, the normal paraffins are blendedwith other species prior to undergoing catalytic isomerization. In someembodiments, the normal paraffins are blended with the isomerizedproduct.

EXAMPLES

The following illustrative examples are intended to be non-limiting.

Example 1 Soybean Oil Feed

Soybean oil was purchased from Lucky Supermarket (El Cerrito, Calif.)under the Sunny Select brand. The soybean feed had an API gravity of21.6 (0.9223 g/mL). The triglycerides of soybean oil are derived mainlyfrom five fatty acids (see, e.g., D. Firestone, Physical and ChemicalCharacteristics of Oils, Fats, and Waxes, 2^(nd) Edition, 2006, AOCSPress, 149). Table 1 discloses the representative ranges of these fattyacids in soybean oil.

TABLE 1 Fatty acid Carbon atoms:Double bonds Weight Percent Palmiticacid 16:0  9.7 to 13.3 Stearic acid 18:0 3.0 to 5.4 Oleic acid 18:1 17.7to 28.5 Linoleic acid 18:2 49.8 to 57.1 α-Linoleic acid 18:3 5.5 to 9.5

Examples 2-8

The soybean oil feed from Example 1 was tested under hydroprocessingconditions in a single reactor over a catalyst based on aNi—Mo—W-maleate catalyst precursor (per Example 1 of U.S. Pat. No.7,807,599) and sulfided with dimethyl disulfide gas (per Example 6 ofU.S. Pat. No. 7,807,599). The reactor conditions included a hydrogen gasrate of 8.0 MSCF/bbl and a LHSV of 1.0 h⁻¹. Additional hydroprocessingconditions are set forth in Tables 2 and 3.

The composition of the whole product was determined by gaschromatography (GC) and is set forth in wt. % in Table 2. All liquidparaffinic products were normal paraffins as determined by GC withnegligible amounts of isoparaffins formed. Methane and propane wereessentially the only other hydrocarbon products. Water, carbon monoxide(CO), and carbon dioxide (CO₂) were by-products from hydrodeoxygenation,hydrodecarbonylation and/or hydrodecarboxylation.

TABLE 2 Composition of the Whole Product in Weight Percent Ex. 2 Ex. 3Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Hydroprocessing Conditions Temperature, °F. 400 450 500 550 500 550 650 Reaction Pressure, psig 1900 1900 19001900 1000 1000 1000 Products Unconverted 75.4 10.9 <0.5 <0.5 <0.5 <0.5<0.5 triglycerides n-C₁₈ paraffin 4.8 27.9 54.2 45.1 46.0 35.1 23.1n-C₁₇ paraffin 0.7 12.0 19.2 26.6 26.9 36.6 46.9 n-C₁₆ paraffin 0.6 3.56.6 6.4 5.7 4.8 3.8 n-C₁₅ paraffin 0.1 1.4 2.3 3.5 3.2 4.9 6.8 C₁₈alcohol 5.8 9.9 — — — — — C₁₆ alcohol 0.6 1.2 — — — — — C₁₈ acid 2.7 4.1— — — — — C₁₆ acid 0.3 0.4 — — — — — C₁₈-C₁₈ ester 3.5 10.2 — — — — —C₁₈-C₁₆ ester 0.9 2.6 — — — — — C₁₆-C₁₆ ester 0.1 0.2 — — — — — Unknownheavies 1.6 2.5 — — — — — Propane 1.2 4.4 4.9 5.0 4.9 5.0 4.8 Methane0.02 0.04 0.2 0.8 0.1 0.2 1.1 H₂O 1.6 6.6 9.8 9.7 8.9 7.5 7.4 CO 0.1 0.70.4 0.4 2.0 2.1 1.8 CO₂ 0.1 1.5 2.4 2.5 2.3 3.8 4.3

With reference to the examples hydroprocessed at 1900 psig andtemperatures of 500° F. and 550° F. (Examples 4 and 5), both theC₁₅/C₁₆n-paraffin and C₁₇/C₁₈ n-paraffin product ratios were 0.35 at500° F. (Example 4). At 550° F. (Example 5), the C₁₅/C₁₆ n-paraffinproduct ratio increased to 0.55 while the C₁₇/C₁₈ n-paraffin productratio increased to 0.59. The increase in the C₁₅/C₁₆ and C₁₇/C₁₈n-paraffin product ratios indicated enhanced selectivity of thiscatalyst for hydrodecarboxylation and/or hydrodecarbonylation (makingC₁₅ and C₁₇ n-paraffins as well as CO and CO₂) over hydrodeoxygenation(making C₁₆ and C₁₈ n-paraffins as well as water) at higher reactiontemperatures. Accordingly, a slightly higher (CO+CO₂)/H₂O product ratiowas achieved at higher temperatures, also reflecting some enhancedselectivity for hydrodecarboxylation and/or hydrodecarbonylation overhydrodeoxygenation.

With reference to the examples hydroprocessed at 1000 psig, the C₁₅/C₁₆n-paraffin product ratio at 500° F. (Example 6) was 0.56 while theC₁₇/C₁₈ n-paraffin ratio was 0.59. At 550° F. (Example 7), the C₁₅/C₁₆n-paraffin product ratio increased to 1.02 while the C₁₇/C₁₈ n-paraffinproduct ratio increased to 1.04. In addition, at 650° F. (Example 8),the C₁₅/C₁₆ n-paraffin product ratio increased to 1.80 while the C₁₇/C₁₈n-paraffin product ratio increased to 2.03. The increase in the C₁₅/C₁₆and C₁₇/C₁₈ n-paraffin product ratios indicated enhanced selectivity ofthis catalyst for hydrodecarboxylation and/or hydrodecarbonylation(making C₁₅ and C₁₇ n-paraffins as well as CO and CO₂) overhydrodeoxygenation (making C₁₆ and C₁₈ n-paraffins as well as water) athigher reaction temperatures. Accordingly, higher (CO+CO₂)/H₂O productratios were achieved at higher temperatures, also reflecting theenhanced selectivity for hydrodecarboxylation and/orhydrodecarbonylation over hydrodeoxygenation.

Furthermore, in comparing the results of Examples 4 and 5 (run at 1900psig) to those of Example 6 and 7 (run at 1000 psig) respectively,enhanced selectivity for hydrodecarboxylation and/orhydrodecarbonylation over hydrodeoxygenation was achieved at lowerreaction pressure, leading to further reduction of hydrogen consumption.

The conversion rate of triglycerides and product selectivity of thehydroprocessing runs are set forth in Table 3.

TABLE 3 Conversion of Triglycerides and Product Selectivity Ex. 2 Ex. 3Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Hydroprocessing Conditions Temperature, °F. 400 450 500 550 500 550 650 Reaction Pressure, psig 1900 1900 19001900 1000 1000 1000 Products Conversion of 24.689.1 >99.5 >99.5 >99.5 >99.5 >99.5 triglycerides, wt. % ProductSelectivity, % n-C₁₈ paraffin 19.3 31.3 54.2 45.1 46.0 35.1 23.1 n-C₁₇paraffin 3.0 13.4 19.2 26.6 26.9 36.6 46.9 n-C₁₆ paraffin 2.4 3.9 6.66.4 5.7 4.8 3.8 n-C₁₅ paraffin 0.3 1.6 2.3 3.5 3.2 4.9 6.8 C₁₈ alcohol23.7 11.2 — — — — — C₁₆ alcohol 2.6 1.3 — — — — — C₁₈ acid 11.1 4.7 — —— — — C₁₆ acid 1.2 0.5 — — — — — C₁₈-C₁₈ ester 14.1 11.5 — — — — —C₁₈-C₁₆ ester 3.7 2.9 — — — — — C₁₆-C₁₆ ester 0.2 0.2 — — — — — Unknownheavies 6.4 2.8 — — — — — Propane 4.9 4.9 4.9 5.0 4.9 5.0 4.8 Methane0.1 0.1 0.2 0.8 0.1 0.2 1.1 H₂O 6.4 7.4 9.8 9.7 8.9 7.5 7.4 CO 0.4 0.80.4 0.4 2.0 2.1 1.8 CO₂ 0.2 1.7 2.4 2.5 2.3 3.8 4.3

For the purposes of this specification and appended claims, unlessotherwise indicated, all numbers expressing quantities, percentages orproportions, and other numerical values used in the specification andclaims, are to be understood as being modified in all instances by theterm “about.” Accordingly, unless indicated to the contrary, thenumerical parameters set forth in the following specification andattached claims are approximations that can vary depending upon thedesired properties sought to be obtained. It is noted that, as used inthis specification and the appended claims, the singular forms “a,”“an,” and “the,” include plural references unless expressly andunequivocally limited to one referent. As used herein, the term“include” and its grammatical variants are intended to be non-limiting,such that recitation of items in a list is not to the exclusion of otherlike items that can be substituted or added to the listed items. As usedherein, the term “comprising” means including elements or steps that areidentified following that term, but any such elements or steps are notexhaustive, and an embodiment can include other elements or steps.

Unless otherwise specified, the recitation of a genus of elements,materials or other components, from which an individual component ormixture of components can be selected, is intended to include allpossible sub-generic combinations of the listed components and mixturesthereof

The patentable scope is defined by the claims, and can include otherexamples that occur to those skilled in the art. Such other examples areintended to be within the scope of the claims if they have structuralelements that do not differ from the literal language of the claims, orif they include equivalent structural elements with insubstantialdifferences from the literal languages of the claims. To an extent notinconsistent herewith, all citations referred to herein are herebyincorporated by reference.

1. A hydrocarbon conversion process, comprising: a) contacting arenewable feedstock, under hydroprocessing conditions, with a bulkcatalyst to form an effluent; and b) recovering a hydrocarbon fractioncomprising normal paraffins from the effluent, wherein thehydroprocessing conditions include a temperature of from 491° F. to 662°F. (255° C. to 350° C.) and a total reaction pressure of from 800 to2000 psig (5.5 to 13.8 MPa gauge).
 2. The process of claim 1, having atriglyceride conversion rate of at least 90 wt. %.
 3. The process ofclaim 1, wherein the feedstock comprises at least 50 wt. %triglycerides.
 4. The process of claim 1, wherein the feedstockoriginates from a biomass source selected from the group consisting ofcrops, vegetables, microalgae, animal fats, and combinations thereof 5.The process of claim 1, wherein the feedstock is selected from the groupconsisting of canola oil, coconut oil, palm oil, palm kernel oil, peanutoil, rapeseed oil, soybean oil, and combinations thereof.
 6. The processof claim 1, wherein the bulk catalyst, prior to sulfidation, isrepresented by the formula:(X)_(b)(Mo)_(c)(W)_(d)O_(f) wherein X is Ni or Co, the molar ratio ofb:(c+d) is 0.5:1 to 3:1, the molar ratio of c:d is >0.01:1, andf=[2b+6(c+d)]/2.
 7. The process of claim 1, wherein the bulk catalyst,prior to sulfidation, is represented by the formula:A_(v)[(M^(P))(OH)_(x)(L)^(n) _(y)]_(z)(M^(VIB)O₄) wherein a) A isselected from the group consisting of an alkali metal cation, anammonium cation, an organic ammonium cation and a phosphonium cation; b)M^(P) is at least one of a Group IIA metal, Group IIB metal, Group IVAmetal, Group VIII metal and combinations thereof, P is oxidation statewith M^(P) having an oxidation state of +2 or +4 depending on theselection of M^(P); c) L is at least one organic oxygen-containingligand, and L has a neutral or negative charge n≦0; d) M^(VIB) is atleast one Group VIB metal having an oxidation state of +6; e)M^(P):M^(VIB) has an atomic ratio between 100:1 and 1:100; f)v−2+P*z−x*z+n*y*z=0;and g) 0<v≦2; 0<x≦P; 0<y≦−P/n; 0<z.
 8. The processof claim 5, wherein M^(P) is Ni and M^(VIB) is selected from the groupconsisting of Mo, W, and combinations thereof, and wherein Ni:(Mo+W) hasa molar ratio of 10:1 to 1:10.
 9. The process of claim 1, wherein thetemperature is from 491° F. to 563° F. (255° C. to 295° C.).
 10. Theprocess of claim 1, wherein the pressure is from 1600 to 2000 psig (11.0to 13.8 MPa gauge).
 11. The process of claim 1, wherein the effluentcomprises at least 75 wt. % of normal paraffins.
 12. The process ofclaim 1, wherein the normal paraffins have from 8 and 24 carbon atoms.13. The process of claim 1, further comprising catalytically-isomerizingat least a portion of the normal paraffins to yield an isomerizedproduct comprising isoparaffins.
 14. The process of claim 13, whereinthe step of catalytically-isomerizing involves an isomerization catalystcomprising a metal selected from the group consisting of Pt, Pd, andcombinations thereof.
 15. The process of claim 13, wherein theisomerized product comprises at least 10 wt. % isoparaffins.
 16. Theprocess of claim 13, wherein the isomerized product has an isoparaffinto normal paraffin mole ratio of at least 5:1.
 17. The process of claim13, wherein the isomerized product has a boiling range of from 250° F.to 1000° F. (121° C. to 538° C.).
 18. The process of claim 13, whereinthe isomerized product has a boiling range of from 280° F. to 572° F.(138° C. to 300° C.).